Compound of sulfonized mineral oils containing formaldehyde and process of making same.



UNITED STATES ATENT OFFICE.

LUDWIG OTTO HELMERS, OF HAMBURG, GERMANY, ASSIGNOR TO IOHTHYOLGESELLSOl-IAFT, CORDES, IIERMANNI (it 00., OF SAME PLACE.

COMPOUND OF SULFON IZED MINERAL OILS CONTAlNlNG FORMALDEHYDE AND PROCESSOF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 674,412, dated May 21,1901. Application filed May 4, 1899. Serial No. 715,559- (No specimens.)

T0 at whom it may concern: 1

Be it known that I,LUDW1G OTTO HELMERS, doctor of philosophy, a subjectof the German Emperor, residing at Hamburg, in the German Empire, haveinvented certain new and useful Improvements in Compounds of SulfonizedMineral Oils Containing Formaldehyde and Processes of Making Same, ofwhich the following is a specification.

My invention relates to the production of odorless and tasteless sulfurcompounds obtained by the action of sulfuric acid or its substitutes onmineral or similar oils containing sulfur in the form of sulfid. Whensulfur compounds of this class-such as thiol, petrosulfol, ichthyol,which are produced by the action of sulfuric acid on mineral oils orsimilar hydrocarbonsare treated with formaldehyde in aqueous solution atordinary temperature, even when left standing for many days, no actiontakes place and the solutions remain perfectly clear. Theysmelldistinctly of formaldehyde, and the original substances can beprecipitated by means of alkali salts. These conditions, however, alterwhen heating for a considerable time is resorted to. By heating anaqueous solution of sulfonic acid or an acidulated solution of one ofthe above-named salts with formaldehyde forseveral hours at 100 there isgradually formed a pasty precipitation. By heating the salts in aneutral or alkaline solution no precipitation takes place; but there isan exception in this regard with ammoniacal salt, as in consequence ofthe reaction of the formaldehyde on the ammonia the reaction soonbecomes sour, whereupon the freed sulfo acids react with the excess offormaldehyde.

Instead of heating the dilute aqueous solution of the initial substancesand formaldehyde in a vessel the reaction products of the formaldehydesmay be obtained by directly evaporating the liquids and then extractingthe residue with water. The reaction prodnot, which, however, in thiscase is difl'icult to clean, remains undissolvedin the evaporating-pan.

The new substance obtained by either one of the methods by treatmentwith formaldehyde forms at first a pasty mass, which during the washingwith water soon assumes a more solid form and which can be dried at 100centigrade withoutmelting. The substance soobtained forms a darkpowder,whicl1 is odorless and tasteless, insoluble in water andin acids,and only slowly decomposed by alkalies. By their behavior towardalkalies they distinctly show their diiference not only from the initialsubstances, which latter completely dissolve in water, as is well known,but also from the albumin (British Patent No. 11,344, of May 6, 1897)and from the gluten (gelatin) combinations of ichthyol and the like,which latter, although insoluble in water and in acids, can be easilydissolved in alkalies while splitting up into their components. Thisalso explains the advantage obtained in therapeutics from the use ofthese new preparations. Consequent on their being difficult to dissolvein alkalineliquids the reaction products ofthe formaldehyde with thepreparations combined with sulfur in the form of sulfid when taken forinternal use become only slowly absorbed, and they thus exercise a weak,but long-enduring eifect.

Example: Two kilograms of a twenty-fiveper-cent. aqueous solution ofichIhyol-sulfonic acid are mixed with one-fourth kilogram fornialine(containing forty per cent. of formaldehyde) and heated for ten hoursover a Water-bath. After cooling the liquid is drawn off from theprecipitation, and this is then repeatedly washed with Water and finallydried at 100 centigrade.

Having fully described my invention, what I claim, and desire to secureby Letters Patent, is

1. The process of producing odorless and tasteless preparations fromsulfonized compounds derived from the reaction of sulfonic o acid uponsulfureted hydrocarbons, which consists in reacting upon such compoundsin acidulated solution with formaldehyde, and heating, whereby atasteless odorless product is obtained containing sulfur, substan-'tially as described.

ALEXANDER SPEoHT,

H. L. MUMMENHOFF.

